Diphenylimidazolines

ABSTRACT

The invention relates to novel diphenylimidazolines of the formula (I)                    
     in which 
     Ar 1 , Ar 2  and R are each as defined in the description, 
     and a plurality of processes for their preparation and to their use for controlling animal pests.

This application is a 371 of PCT/EP99/04682 filed Jul. 6, 1999.

The invention relates to novel diphenylimidazolines, to processes fortheir preparation and to their use for controlling animal pests.

Hitherto, only few 2,4-diaryl-4,5-dihydroimidazoles, which areoptionally substituted at nitrogen and in the aryl radicals, have beenknown. The parent compound, 2,4-diphenyl-4,5-dihydro-1H-imidazole wassynthesized as early as the 19th century (Chem. Ber. 28, 3172 (1895)).Furthermore, Tetrahedron 29, 3137 (1973) describes theN-methoxycarbamate, SU 466231 (cited in C.A. 83:79277) describes theN-cyclohexyl derivative, EP-A 10 852 describes the N-hydroxyethylderivative and, finally, Synlett 10, 1031 (1995) describes the2-para-methyl-4-para-methoxy derivative which is substituted in bothphenyl rings and the corresponding mono-substituted compounds. Finally,two compounds which are formally derived from the tautomeric3H-imidazole are described,5-(3,4-dimethylphenyl)-1-methyl-2-phenyl-4,5-dihydro-1H-imidazole inPol. Ann. Univ. Mariae Curie-Skiodowska, Sect. D 36, 111 (1981) and2-hydroxyphenyl-1-methyl-5-phenyl-4,5-dihydro-1H-imidazole in Proc.Indian Acad. Sci., Chem. Sci. 104, 383 (1992). Without concreteexamples, diphenylimidazolines are described in other patentapplications: BE 695 703; BE 839 503; BE 846 373; DD 155296 (cited inC.A. 98:57781); DOS 25 12 513; DOS 27 38 270; DOS 29 46 085; DOS 32 04333; DOS 32 11 301; DOS 32 36 598; DOS 36 10 758; DOS 40 17 801; DOS 4235 590; EP-A 1 468; EP-A1 516 982; EP-A2 617 069; FR-A1 2629092; JP-A 5690982 (cited in C.A. 96:147323); JP-A 56 90983 (cited in C.A.96:147322); JP-A 58 152085 (cited in C.A. 100:213975); JP-A 59 116660(cited in C.A. 102:36786); JP-A2 62 195369 (cited in C.A. 108:167467)JP-A 04 180944 (cited in C.A. 118:23600); U.S. Pat. No. 3,202,674; U.S.Pat. No. 4,066,625; U.S. Pat. No. 4,661,600; WO 93/04045; WO 93/04046;derivatives which are substituted in both phenyl rings are described inDOS 27 01 372 (only methyl or ethyl substituents), DOS 32 17 875 (if theC₆-C₁₅-aryl radical is understood as, for example, tolyl or xylyl), inU.S. Pat. No. 4,389,371 and U.S. Pat. No. 4,452,758 (exclusively alkalimetal salts of N-(alkoxy)-alkyl-carboxylic acids) and DOS 27 44 782 andEP-A1 596 326 (specific heterocyclylmethyl substituent).

Hitherto, nothing has been known concerning the use of2,4-diaryl-4,5-dihydroimidazoles as pesticides.

This invention, accordingly, provides novel diarylimidazolines of theformula (I)

in which

Ar¹ represents the grouping (a)

 in which

R¹ represents halogen, alkyl, alkoxy or halogenoalkoxy and

R² represents hydrogen, halogen, alkyl or alkoxy,

Ar² represents the grouping (b) or (c)

 in which

R³, R⁴, R⁵ and R⁶ independently of one another each represent hydrogen,halogen, alkyl, alkoxy, halogenoalkoxy or halogenoalkylthio,

R⁷ represents hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy or halogenoalkylthio and

Y represents a direct bond, oxygen, methylene, —O—CH₂— or —CH₂O— and

R represents cyano, alkoxyalkyl, formyl, alkylcarbonyl, alkoxycarbonylor —C(X)—NHR⁸ in which

X represents oxygen or sulphur and

R⁸ represents hydrogen or alkyl.

Here, halogen represents F, Cl, Br and iodine, in particular F, Cl andBr.

The compounds of the formula (I) include N-substituted derivatives ofthe two tautomeric forms of the cyclic imidate function which forms thebasis for the imidazoline. These compounds are 1H-4,5-dihydroimidazolesof the formula (I)_(a) and 3H-4,5-dihydroimidazoles of the formula(I)_(b) which is intended to be expressed by the dotted line in theformula (I).

The compounds of the formulae (I)_(a) and (I)_(b) can be present both asmixtures or in the form of the pure isomers and furthermore, depending,inter alia, on the kind of substituents, as geometric and/or opticalisomers or isomer mixtures of varying composition. These isomers can, ifappropriate, be separated in a customary manner. The invention relatesboth to the pure isomers and to their mixtures.

Furthermore, it has been found that the novel compounds of the formula(I) are obtained by one of the processes described below.

A) Diphenylimidazolines of the formula (I-a)

 in which

Ar¹ and Ar² are each as defined above and

R⁹ represents C₁-C₄-alkyl,

are obtained by condensing β-chlorocarbamates of the formula (II)

 in which

Ar² and R⁹ are each as defined above

with benzonitriles of the formula (III)

 Ar¹—CN  (III),

 in which

Ar¹ is as defined above in the presence of sulphuric acid, or

B) diphenylimidazolines of the formula (I-b)

 in which

R is as defined above and

R¹⁻¹ represents fluorine, chlorine, alkyl, alkoxy or halogenoalkoxy,

R²⁻¹ represents hydrogen, fluorine, chlorine, alkyl or alkoxy,

R⁵⁻¹ and R⁶⁻¹ independently of one another each represent hydrogen,fluorine, chlorine, alkyl, alkoxy, halogenoalkyl or halogenoalkylthioand

R⁷⁻¹ represents hydrogen, fluorine, chlorine, cyano, alkyl, alkoxy,alkylthio, halogenoalkyl or halogenoalkylthio

are obtained by coupling halogen compounds of the formula (I-c)

 in which

R, R¹⁻¹, R²⁻¹ and R⁵⁻¹ are each as defined above and

Z represents bromine or iodine

with boronic acids of the formula (IV)

 in which

R⁶⁻¹ and R⁷⁻¹ are each as defined above

in the presence of a catalyst and, if appropriate, in the presence of anacid binder and, if appropriate, in the presence of a diluent, or

C) diphenylimidazolines of the formula (I)

 in which

Ar¹, Ar² and R are each as defined above

are obtained by condensing diphenylimidazolines of the formula (V)

 which are not substituted at nitrogen and in which

Ar¹ and Ar² are each as defined above

with compounds of the formula (VI)

R—X¹  (VI),

 in which

R is as defined above and

X¹ represents, depending on the radical R, a suitable leaving group,such as —Cl, —Br, —OSO₂OR¹⁰ or —OR¹⁰

in which

R¹⁰ represents alkyl or aryl,

if appropriate in the presence of a reaction auxiliary, or

D) diphenylimidazolines of the formula (I-d)

 in which

Ar¹, Ar² and X are each as defined above

are obtained by reacting nitrites of the formula (I-e)

 in which

Ar¹ and Ar² are each as defined above

with water or hydrogen sulphide, if appropriate in the presence of areaction auxiliary.

Furthermore, it has been found that the compounds of the formula (I) andtheir biologically active salts are suitable for controlling animalpests, in particular insects, arachnids and nematodes.

The formula (I) provides a general definition of the novel compounds.Preferred substituents or ranges of the radicals listed in the formulaementioned hereinabove and hereinbelow are illustrated below.

Ar¹ particularly represents the grouping (a)

Ar² particularly represents the grouping (b) or (c)

R particularly represents cyano, C₁-C₄-alkoxy-C₁-C₄-alkyl,C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl or —C(X)—NHR⁸.

R¹ particularly represents halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy orC₁-C₃-halogenoalkoxy.

R² particularly represents hydrogen, halogen, C₁-C₃-alkyl orC₁-C₃-alkoxy.

R³, R⁴, R⁵ and R⁶ independently of one another each particularlyrepresent hydrogen, halogen, C₁-C₁₂-alkyl or C₁-C₁₂-alkoxy.

R⁷ particularly represents hydrogen, halogen, cyano, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-halogenoalkyl, C₁-C₄-halogenoalkoxyor C₁-C₄-halogenoalkylthio.

R⁸ particularly represents hydrogen or C₁-C₄-alkyl.

X particularly represents oxygen or sulphur.

Y particularly represents a direct bond or oxygen.

Here, halogen preferably represents F, Cl, Br and iodine, in particularF, Cl and Br.

Ar¹ particularly preferably represents the grouping (a)

Ar² particularly preferably represents the grouping (b-a) or (c-a)

R particularly preferably represents cyano, C₁-C₃-alkoxy-C₁-C₃-alkyl,C₁-C₃-alkylcarbonyl, C₁-C₂-alkoxycarbonyl or —C(X)—NHR⁸.

R¹ particularly preferably represents fluorine, chlorine, bromine,iodine, C₁-C₃-alkyl and C₁-C₃-alkoxy.

R² particularly preferably represents hydrogen, fluorine, chlorine,bromine, C₁-C₃-alkyl or C₁-C₃-alkoxy.

R³, R⁴, R⁵ and R⁶ independently of one another each particularlypreferably represent hydrogen, fluorine, chlorine, bromine, iodine,C₁-C₆-alkyl or C₁-C₆-alkoxy.

R⁷ particularly preferably represents hydrogen, fluorine, chlorine,bromine, iodine, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio,fluorine- or chlorine-substituted C₁-C₄-alkyl, C₁-C₄-alkoxy orC₁-C₄-alkylthio.

R⁸ particularly preferably represents hydrogen or C₁-C₄-alkyl.

X particularly preferably represents oxygen or sulphur.

Ar¹ very particularly preferably represents the grouping (a-1), (a-2) or(a-3)

Ar² very particularly preferably represents the grouping (b-b) or (c-b)

R very particularly preferably represents cyano, ethoxymethyl, acetyl,propionyl, butyryl, methoxycarbonyl, ethoxycarbonyl or —C(X)—NHR⁸.

R¹ very particularly preferably represents fluorine, chlorine, bromine,methyl, ethyl, methoxy or ethoxy.

R² very particularly preferably represents hydrogen, fluorine, chlorine,bromine, methyl, ethyl, methoxy or ethoxy.

R³, R⁴, R⁵ and R⁶ independently of one another each very particularlypreferably represent hydrogen, fluorine, chlorine, bromine, methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,pentyl, hexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy, tert-butoxy, pentyloxy or hexyloxy.

R⁷ very particularly preferably represents fluorine, chlorine, bromine,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio,isopropylthio, difluoromethyl, trifluoromethyl, dichloromethyl,trichloromethyl, difluoromethoxy, trifluoromethoxy,chlorodifluoromethoxy, 1,1-difluoroethoxy, 1,1,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy,2,2,2-trichloro-1,1-difluoroethoxy, pentafluoroethoxy,difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio,1,1-difluoroethylthio, 1,1,2-trifluoroethylthio,2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio,2-chloro-1,1,2-trifluoroethylthio, 2,2,2-trichloro-1,1-difluoroethylthioor pentafluoroethylthio.

R⁸ very particularly preferably represents hydrogen, methyl or ethyl.

X very particularly preferably represents oxygen of sulphur.

Ar¹ in particular very particularly preferably represents the grouping(a-3)

Ar² in particular very particularly preferably represents the grouping(b-c)

R¹ and R² are identical or different and in particular very particularlypreferably represent hydrogen, F, Cl, CH₃ or ethyl, where R¹ and R² arenot simultaneously hydrogen.

R³ in particular very particularly preferably represents bromine,substituted phenyl or phenoxy, suitable substituents being —OCF₃, —SCF₃or t-butyl.

R in particular very particularly preferably represents methyl, ethyl,propyl, i-propyl, cyano,

Ar¹ very especially particularly preferably represents the grouping(a-3)

Ar² very especially particularly preferably represents the grouping(b-c)

R¹ and R² are identical or different and very especially particularlypreferably represent F, Cl and hydrogen, where R¹ and R² do notsimultaneously represent hydrogen.

R³ very especially particularly preferably represents bromine or4-trifluoromethoxyphenyl.

R very especially particularly preferably represents

The abovementioned general or preferred radical definitions orillustrations can be combined with each other at will, i.e. includingcombinations between the respective ranges and preferred ranges. Theyapply both to the end products and, correspondingly, to the precursorsand intermediates.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

In particular very particularly preferred according to the invention arethe compounds of the formula (I) which contain a combination of themeanings listed above as being in particular very particularlypreferred.

Very especially particularly preferred according to the invention arethe compounds of the formula (I) which contain a combination of themeanings listed above as being very especially particularly preferred.

Saturated or unsaturated hydrocarbon radicals such as alkyl can in eachcase be straight-chain or branched, including in combination withheteroatoms, such as, for example, in alkoxy.

Optionally substituted radicals may be mono- or polysubstituted, and inthe case of polysubstitution, the substituents may be identical ordifferent.

Using, for example, ethyl N-[2-chloroethyl-2-(3-methylphenyl)]-carbamateand 2-propylbenzonitrile as starting materials, the course of thereaction of the process (A) according to the invention can berepresented by the following equation:

Using, for example,4-(4-bromophenyl)-1-ethoxycarbonyl-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazoleand 4-methylphenylboronic acid as starting materials, the course of thereaction in the process (B) according to the invention can berepresented by the following equation:

Using, for example,4-(2-chlorophenyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole andN-methylcarbamoyl chloride as starting materials, the course of thereaction of the process (C) according to the invention can berepresented by the following equation:

Reacting, for example,4-(2-chlorophenyl)-1-cyano-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazoleas starting material with aqueous sulphuric acid, the course of thereaction of the process (D) according to the invention can berepresented by the following equation:

The formula (II) provides a general definition of the β-chlorocarbamatesrequired for carrying out the process (A) according to the invention. Inthis formula, Ar² and R⁹ preferably have those meanings which havealready been mentioned as being preferred in connection with thedescription of the diarylimidazolines of the formula (I).

β-chlorocarbamates of the formula (II) can be prepared, for example, byadding ethyl N,N-dichlorocarbamates of the formula (VII) to styrenes ofthe formula (VIII) in a dipolar-aprotic solvent such as, for example,acetonitrile, at temperatures between −20 and +20° C., anddehalogenating the N-chlorocarbamide which is initially formed with areducing agent such as, for example, bisulphite solution, according tothe equation below:

Some of the ethyl N,N-dichlorocarbamates of the formula (VII) arecommercially available, known from the literature or obtainable by knownprocesses (see, for example, Thomas A. Foglia, Daniel Swern, J. Org.Chem. 31 (1966) 3625-3631; Ronald E. White, Peter Kovacic, J. Am. Chem.Soc. 97 (1975) 1180-1184).

The formula (III) provides a general definition of the benzonitrilesfurthermore required for carrying out the process (A) according to theinvention. In this formula, Ar¹ preferably has that meaning which hasalready been mentioned in connection with the description of thediarylimidazolines of the formula (I) as being preferred.

The benzonitriles of the formula (III) and the styrenes of the formula(VIII) are generally known compounds of organic chemistry (see textbooksof organic chemistry, such as, for example, Beyer-Walter, Lehrbuch derorganischen Chernie, 21st edition, 1988), and some of them arecommercially available.

The halogen compounds of the formula (I-c) required for carrying out theprocess (B) according to the invention are a subset of the compounds ofthe general formula (I) according to the invention and can be prepared,for example, according to processes (A), (C) or (D).

The formula (IV) provides a general definition of the boronic acidsfurthermore required for carrying out the process (B) according to theinvention. In this formula, R⁶⁻¹ and R⁷⁻¹ preferably have those meaningswhich have already been mentioned in connection with the description ofthe diarylimidazolines of the formula (I) as being preferred, except forbromine and iodine.

Some of the aromatic boronic acids of the formula (IV) are commerciallyavailable, and are known from the literature, or they can be preparedsimilarly to known methods [cf. Chem. Rev. 45, 2457 (1995); Pure Appl.Chem. 66, 213 (1994)].

The formula (V) provides a general definition of the diarylimidazolinesrequired for carrying out the process (C) according to the invention. Inthis formula, Ar¹ and Ar² preferably have those meanings which havealready been mentioned in connection with the description of theN-substituted diarylimidazolines of the formula (I) as being preferred.The diarylimidazolines of the formula (V) are novel and likewise formpart of the subject-matter of the present application.

Diarylimidazolines of the formula (V) can be prepared, for example, bycleaving carbamates of the formula (I-a) with alkali metal hydroxidessuch as, for example, potassium hydroxide in the presence of asolubilizer such as, for example, ethanol at temperatures of from 20 to120° C., according to the following equation:

The carbamates of the formula (I-a) are a subset of the compounds of thegeneral formula (I) according to the invention and can be prepared, forexample, according to process (A).

The N-cyanodiphenylimidazolines of the formula (I-d) required forcarrying out the process (D) according to the invention are a subset ofthe compounds of the general formula (I) according to the invention andcan be prepared, for example, according to process (C).

The process (A) according to the invention is carried out in thepresence of (aqueous) sulphuric acid. In general, the process is carriedout at concentrations of from 80 to 100%.

In the case of the process (A) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between −20° C. and +50° C.,preferably between 0 and 30° C.

When carrying out the process (A) according to the invention, generally0.5 to 3 mol, preferably 1 to 2 mol, of benzonitrile of the formula(III) is employed per mole of β-chlorocarbamate of the formula (II).Here, the acid is employed in a large, for example 2- to 20-fold,excess, and, if appropriate, the reaction is carried out using the acidas solvent.

For carrying out the process (B) according to the invention, palladiumcomplexes are suitable for use as catalysts. Preferred catalysts are,for example, tetrakis (triphenylphosphine)palladium anddichloro-bis(triphenylphosphine)palladium.

Suitable acid acceptors for carrying out the process (B) according tothe invention are inorganic or organic bases. These preferably includealkaline earth metal or alkali metal hydroxides, acetates, carbonates orbicarbonates, such as, for example, sodium hydroxide, potassiumhydroxide, barium hydroxide or ammonium hydroxide, sodium acetate,potassium acetate, calcium acetate or ammonium acetate, sodiumcarbonate, potassium carbonate or ammonium carbonate, sodium bicarbonateor potassium bicarbonate, alkali metal fluorides, such as, for example,caesium fluoride, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,

N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the process (B) according to theinvention are water, organic solvents and mixtures of these. Examplesinclude: aliphatic, alicyclic or aromatic hydrocarbons, such as, forexample, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; halogenatedhydrocarbons, such as, for example, chlorobenzene, dichlorobenzene,methylene chloride, chloroform, carbon tetrachloride, dichloro-trichloroethane or tetrachloroethylene; ethers, such as, for example,diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole;alcohols, such as, for example, methanol, ethanol, n- or iso-propanol,n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol,ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether; water.

In the case of the process (B) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between 0° C. and +140° C.,preferably between 50° C. and +100° C.

When carrying out the process (B) according to the invention, theboronic acid of the formula (IV) and the halogen compound of the formula(I-c) are employed in a molar ratio of from 1:1 to 3:1, preferably from1:1 to 2:1. In general, 0.005 to 0.5 mol, preferably 0.01 mol to 0.1mol, of catalyst are employed per mole of the compound of the formula(I-c). In general, an excess of base is employed.

The process (C) according to the invention is carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all customary inorganic or organic bases. These preferably includealkaline earth metals or alkali metal hydrides, hydroxides, amides,alkoxides, acetates, carbonates or bicarbonates, such as, for example,sodium hydride, sodium hydroxide, potassium hydroxide or ammoniumhydroxide, sodium amide, lithium diisopropylamide, sodium methoxide,sodium ethoxide, potassium tert-butoxide, sodium acetate, potassiumacetate, calcium acetate or ammonium acetate, sodium carbonate,potassium carbonate or ammonium carbonate, sodium bicarbonate orpotassium bicarbonate, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

If appropriate, the process (C) according to the invention can becarried out in the presence of a suitable phase-transfer catalyst.Examples of such catalysts include: tetrabutylammonium iodide,tetrabutylammonium bromide or tetrabutylammonium chloride,tributylmethylphosphonium bromide, trimethyl-C₁₃/C₁₅-alkylammoniumchloride or trimethyl-C₁₃/C₁₅-alkylammonium bromide,dibenzyldimethylammonium methylsulphate,dimethyl-C₁₂/C₁₄-alkylbenzylammonium chloride, 15-crown-5, 18-crown-6 ortris[2-(2-methoxyethoxy)-ethyl]-amine.

The process (C) according to the invention is preferably carried out inthe presence of a diluent. Suitable diluents are water, organic solventsand any mixtures of these. Examples include: aliphatic, alicyclic oraromatic hydrocarbons, such as, for example, petroleum ether, hexane,heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene ordecalin; halogenated hydrocarbons, such as, for example, chlorobenzene,dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride,dichloro-, trichloroethane or tetrachloroethylene; ethers, such as, forexample, diethyl ether, diisopropyl ether, methyl t-butyl ether, methylt-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole;ketones, such as, for example, acetone, butanone, methyl isobutyl ketoneor cyclohexanone; nitriles, such as, for example, acetonitrile,propionitrile, n- or iso-butyronitrile or benzonitrile; amides, such as,for example, formamide, N,N-dimethylformamide, N,N-dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorictriamide; N-oxides, such as N-methylmorpholine N-oxide; esters, such as,for example, methyl acetate, ethyl acetate or butyl acetate;sulphoxides, such as, for example, dimethyl sulphoxide; sulphones, suchas sulpholane; alcohols, such as, for example, methanol, ethanol, n- oriso-propanol, n-, iso-, sec- or tert-butanol, ethanediol,propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether; water.

In the case of the process (C) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between −20° C. and +100°C., preferably between 0° C. and 60° C.

When carrying out the process (C) according to the invention, in generalfrom 1 to 5 mol of the compound of the formula (VI) are employed permole of the compound of the formula (V). However, whenever it isexpedient, for example in the case of a gaseous reagent, it is possibleto employ a larger excess of the compound of the formula (VI).

The process (D) according to the invention is carried out in thepresence of a reaction auxiliary. When reacting with hydrogen sulphide,use is made, for example, of tertiary amines, such as pyridine ortriethylamine. These may simultaneously serve as diluents. In thereaction with water, use is made, for example, of aqueous mineral acids,such as sulphuric acid or hydrochloric acid, preferably 96% strengthsulphuric acid. The acids may likewise simultaneously serve as diluent.

In the case of the process (D) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between −20° C. and +100°C., preferably between 0° C. and 60° C.

The amount of hydrogen sulphide or water employed when carrying out theprocess (D) according to the invention is not critical. At least 1 molof hydrogen sulphide or water is required per mole of nitrile of theformula (I-e). In the case of hydrogen sulphide, it is advantageous toemploy a larger excess.

The reactions of the processes (A to D) according to the invention canbe carried out at atmospheric pressure or under elevated pressure.Preference is given to carrying out the processes at atmosphericpressure. The practice of the reactions, the work-up and the isolationof the reaction products is carried out according to customary, knownmethods. The end products are preferably purified by crystallization,chromatographic separation or by removing the volatile components, ifappropriate under reduced pressure (cf. also the preparation examples).

The active compounds, having good crop tolerance and favourablehomeotherm safety, are suitable for controlling animal pests, inparticular insects, arachnida and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene field. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus human corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp, Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyarni, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus sernipenetrans,Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp.,Xiphinema spp. and Trichodorus spp.

The active compounds of the formula (I) according to the invention have,in particular, excellent activity against the larvae of the mustardbeetle (Phaedon cochleariae), against the caterpillars of the owlet moth(Spodoptera frugiperda) and against all stages of the greenhouse redspider mite (Tetranychus urticae).

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents, forexample, can also be used as auxiliary solvents. Suitable liquidsolvents are in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as finely divided silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite as well as synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks; suitableemulsifying and/or foam-forming agents are: for example nonionic andanionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well asprotein hydrolysates; dispersing agents suitable are: for examplelignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colourants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas, substances produced bymicroorganisms, etc.

Examples of particularly advantageous mixture components are thefollowing compounds:

Fungicides:

2-aminobutane; 2-anilino4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxamide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyirnino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]-acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon,

edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulphamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulphocarb, methfuroxam, metirarn, metsulphovax,myclobutanil,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin,piperalin, polycarbamate, polyoxin, probenazole, prochloraz,procyrnidone, propamocarb, propiconazole, propineb, pyrazophos,pyrifenox, pyrimethanil, pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/acaricides/nematicides:

abamectin, acephate, acetarniprid, acrinathrin, alanycarb, aldicarb,aldoxycarb, alpha-cypermethrin, alphamethrin, arnitraz, avermectin, AZ60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophosA, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb,clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin,cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos,diofenolan, disulfoton, docusat-sodium, dofenapyn,

eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole,etrimfos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb,fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin,fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron,flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox,furathiocarb,

granulosis viruses,

halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,

imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

nuclear polyhedrosis viruses,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, metaldehyde, methamidophos, Metharhiziumanisopliae, Metharhizium flavoviride, methidathion, methiocarb,methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoate, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur,prothiofos, prothoate, pymetrozine, pyraclofos, pyresmethrin, pyrethrum,pyridaben, pyridathion, pyrimidifen, pyriproxyfen,

quinalphos,

ribavirin,

salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, terivinphos, terbufos,tetrachlorvinphos, theta-cypernethrin, thiapronil, thiatriphos,thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin,tralocythrin, tralomethrin, triarathene, triazamate, triazophos,triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,

varmidothion, vaniliprole, Verticillium lecanii,

YI 5302,

zeta-cypermethrin, zolaprofos,

(1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,

1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,

2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]4,5-dihydro-oxazole,

2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,

2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,

2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,

3-methylphenyl propylcarbamate.

4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,

4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,

4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,

4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,

Bacillus thuringiensis strain EG-2348,

[2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,

2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-ylbutanoate,

[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,

dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,

ethyl[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,

N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,

N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,

N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,

N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

A mixture with other known active compounds such as herbicides, or withfertilizers and growth regulators is also possible.

The active compound according to the invention can furthermore bepresent in its commercially available formulations and in the use formsprepared from these formulations, as a mixture with synergistic agents.Synergistic agents are compounds which increase the action of the activecompounds without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide ranges. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene and stored-product pests, the active compoundis distinguished by an excellent residual action on wood and clay aswell as a good stability to alkali on limed substrates.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites),such as ixodid ticks, argasid ticks, scab mites, trombiculid mites,flies (stinging and sucking), parasitic fly larvae, lice, hair lice,bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola

From the order Diptera and the sub-orders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phiebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneu-monyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compounds of the formula (I) according to the invention show,for example, excellent activity against all larval stages of the flyLucillia cuprina.

The active compounds according to the invention are also suitable forcontrolling arthropods which attack agricultural livestock, such as, forexample, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo,rabbits, chickens, turkeys, ducks, geese, honey bees, other domesticanimals, such as, for example, dogs, cats, cage birds, aquarium fish,and so-called experimental animals such as, for example, hamsters,guinea-pigs, rats and mice. By controlling these arthropods, it isintended to reduce mortality and decreased performance (in meat, milk,wool, hides, eggs, honey etc.), so that more economical and simpleranimal keeping is made possible by using the active compounds accordingto the invention.

In the veterinary sector, the active compounds according to theinvention are used in a known manner by enteral administration, forexample in the form of tablets, capsules, drinks, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration, such as, for example, by means of injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal application, by dermal administration, forexample in the form of dipping or bathing, spraying, pouring-on andspotting-on, washing, dusting, and with the aid of shaped articles whichcomprise active compound, such as collars, ear tags, tail marks, limbbands, halters, marking devices, etc.

When administered to livestock, poultry, domestic animals etc., theactive compounds of the formula (I) can be used as formulations (forexample powders, emulsions, flowables) which comprise the activecompounds in an amount of 1 to 80% by weight, either directly or afterdilution by a factor of 100 to 10,000, or they may be used in the formof a chemical bath.

Furthermore, it has been found that the compounds of the formula (I)according to the invention have a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and as beingpreferred, but without any limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobiusmollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctusplanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale,Minthes rugicollis, Zyleborus spec., Tryptodendron spec., Apatemonachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylonspec., Dinoderus minutus.

Dermapterans, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials are to be understood as meaning, in the presentcontext, non-living materials such as, preferably, synthetic materials,glues, sizes, paper and board, leather, wood and timber products, andpaint.

The materials to be protected very particularly against attack byinsects are wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention or mixtures comprising such a composition areto be understood as meaning, for example, construction timber, woodenbeams, railway sleepers, bridge components, jetties, wooden vehicles,boxes, pallets, containers, telephone poles, wood lagging, windows anddoors made of wood, plywood, particle board, joiner's articles, or woodproducts which, quite generally, are used in the construction of housesor in joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations, such as powders, granules, solutions,suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersant and/or binder or fixative, waterrepellent, if appropriate desiccants and UV stabilizers and, ifappropriate, colourants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for the protection ofwood and wooden materials comprise the active compound according to theinvention at a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thespecies and the occurrence of the insects and on the medium. The optimumrate of application can be determined upon use in each case by testseries. However, in general, it suffices to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be protected.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-type organochemical solvent or solventmixture of low volatility and/or a polar organochemical solvent orsolvent mixture and/or water and, if appropriate, an emulsifier and/orwetting agent.

Organochemical solvents which are preferably employed are oily oroil-type solvents having an evaporation number of above 35 and aflashpoint of above 30° C., preferably above 45° C. Substances which areused as such oily and oil-type solvents which have low volatility andare insoluble in water are suitable mineral oils or their aromaticfractions, or mineral-oil-containing solvent mixtures, preferably whitespirit, petroleum and/or alkylbenzene.

Substances which are advantageously used are mineral oils with a boilingrange of 170 to 220° C., white spirit with a boiling range of 170 to220° C., spindle oil with a boiling range of 250 to 350° C., petroleumor aromatics of boiling range 160 to 280° C., essence of turpentine andthe like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-type solvents of low volatility having anevaporation number of above 35 and a flashpoint of above 30° C.,preferably above 45° C., can be partially replaced by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture likewise has an evaporation number of above 35 and a flashpointof above 30° C., preferably above 45° C., and that theinsecticide/fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, part of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Substances which are preferably used are aliphaticorganochemical solvents having hydroxyl and/or ester and/or ethergroups, such as, for example, glycol ether, esters and the like.

The organochemical binders used within the scope of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se and can be diluted with water and/or are soluble ordispersible or emulsifiable in the organochemical solvents employed, inparticular binders composed of, or comprising, an acrylate resin, avinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenol resin, hydrocarbon resin, such asindene/coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Up to 10% by weight of bitumen orbituminous substances can also be used as binders. In addition,colourants, pigments, water repellents, odour-masking substances andinhibitors or anticorrosives known per se and the like can be employed.

The composition or the concentrate preferably comprises, in accordancewith the invention, at least one alkyd resin or modified alkyd resinand/or a drying vegetable oil as the organochemical binder. Preferablyused according to the invention are alkyd resins with an oil content ofover 45% by weight, preferably 50 to 68% by weight.

All or some of the abovementioned binder can be replaced by a fixative(mixture) or a plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of binder employed).

The plasticizers are from the chemical classes of phthalic esters, suchas dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate,phosphoric esters, such as tributyl phosphate, adipic esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or relativelyhigh-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

Fixatives are chemically based on polyvinyl alkyl ethers, such as, forexample, polyvinyl methyl ether, or ketones, such as benzophenone orethylene benzophenone.

Particularly suitable as a solvent or diluent is also water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective protection of wood is achieved by large-scaleindustrial impregnation processes, for example vacuum, double-vacuum orpressure processes.

If appropriate, the ready-to-use compositions can additionally compriseother insecticides and, if appropriate, additionally one or morefungicides.

Suitable additional components which may be admixed are, preferably, theinsecticides and fungicides mentioned in WO 94/29 268. The compoundsmentioned in that document are expressly part of the presentapplication.

Very particularly preferred components which may be admixed areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorofluanid, tolylfluanid,3-iodo-2-propinylbutyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention can be seen from the examples below.

PREPARATION EXAMPLES Example I-1

3.1 g (10 mmol) of ethyl N-[2-(4-bromophenyl)-2-chloroethyl]-carbamate(for example from Example II-1) and 2.09 g (15 mmol) of2,6-difluorobenzonitrile were dissolved in 10 ml of conc. sulphuric acidand stirred at room temperature for three hours, during which the colourof the solution turned dark. After this, the mixture was carefullypoured onto ice. It was extracted 2x with dichloromethane and theaqueous phase was made alkaline with sodium hydroxide and once moreextracted. The combined organic phases were extracted with saturatedsodium chloride solution, dried and concentrated. The 4.4 g of crudeproduct which had been obtained were chromatographed over a silica gelcolumn (cyclohexane: ethyl acetate=5:1). This gave 3.6 g (88% of theory)of4-(4-bromophenyl)-1-ethoxycarbonyl-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazolas a viscous yellow oil.

¹H NMR (400 MHz, CDCl₃): δ [ppm] 1.1 (t, 3H); 3.7 (m, 1H); 4.1 (q, 2H);4.4 (m, 1H); 5.4 (m, 1H); 6.9-7.6 (m, 7H).

Example I-2

By the method of Example I-1, 3.1 g (10 mmol) of ethylN-[2-(4-bromophenyl)-2-chloroethyl]-carbamate (for example from ExampleII-1) and 2.1 g of (15 mmol) 2-chlorobenzonitrile gave 2.9 g (72% oftheory) of4-(4-bromophenyl)-2-(2-chlorophenyl)-1-ethoxycarbonyl-4,5-dihydro-1H-imidazoleas a viscous colourless oil.

¹H NMR (400 MHz, CDCl₃): δ [ppm] 1.0 (t, 3H); 3.9 (m, 1H); 4.0 (q, 2H);4.4 (m, 1H); 5.3 (m, 1H); 7.2-7.6 (m, 8H).

Example I-3

3.6 g (9 mmol) of4-(4-bromophenyl)-1-ethoxycarbonyl-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(for example from Example I-1) were dissolved in 25 ml ofdimethoxyethane and admixed with 20 ml of a 1M solution of sodiumcarbonate. 2.9 g (11 mmol) of 4-trifluoromethoxyphenylboronic acid (85%strength) and finally, as catalyst, 336 mg (0.48 mmol) ofdichloro-bis(triphenylphosphino)palladium(II) were added to thismixture. The mixture, which was initially yellow, was heated at reflux,giving a brown solution. The mixture was boiled overnight and, aftercooling, admixed with water and extracted with ethyl acetate. Thecombined extracts were washed successively with ammonium chloridesolution, water and sodium chloride solution, concentrated andchromatographed over a silica gel column (cyclohexane:ethylacetate=10:1). This gave 2.50 g (57% of theory) of1-ethoxycarbonyl4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluoro-phenyl)-4,5-dihydro-1H-imidazole.

M.p.: 105-107° C.

Example I-4

By the method of Example I-3, 1.5 g (9.0 mmol) of4-(4-bromophenyl)-2-(2-chloro-phenyl)-1-ethoxycarbonyl4,5-dihydro-1H-imidazole(for example from Example I-2) and 1.0 g (4.8 mmol) of4-trifluoromethoxyphenylboronic acid gave 1.38 g (76% of theory) of2-(2-chlorophenyl)-1-ethoxycarbonyl-4-(4′-trifluormethoxy-4-biphenylyl)-4,5-dihydro-1H-imidazoleas a colourless oil.

¹H NMR (400 MHz, CDCl₃): δ [ppm] 1.0 (t, 3H); 3.9 (m, 1H); 4.0 (q, 2H);4.4 (m, 1H); 5.4 (m, 1H); 7.2-7.6 (m, 12H).

Example I-5

At 5° C., 22.9 g (0.37 mol) of cyanogen chloride were introduced into asolution of 2.6 g (6.1 mmol) of4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(for example from Example V-1) in 260 ml of dichloro-methane. Themixture was stirred at 0-5° C. for 45 minutes. Subsequently, a solutionof 15.6 g (0.39 mol) of sodium hydroxide in 140 ml of water (10%strength base) was added dropwise. The organic phase was removed and theaqueous phase was then extracted with dichloromethane, and the combinedorganic phases were washed with water, dried and concentrated underwater-pump vacuum (30° C.). This gave 2.9 g of crude product which wereseparated by column chromatography (silica gel Ø=3 cm, 1=30 cm; gradientcyclohexane: ethyl acetate 7:1→5:1). This gave 1.55 g (57% of theory) of1-cyano-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(I-5a) and 0.80 g (30% of theory) of3-cyano-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-3H-imidazole(I-5b).

(I-5a): m.p.: 123-124° C; (I-5b): ¹H NMR (500 MHz, DMSO): δ [ppm] 4.1(m, 1H); 4.7 (m, 1H); 5.7 (m, 1H); 7.4-7.9 (m, 11H).

Example I-6

At 0° C., a solution of 1.5 g (3.6 mmol) of4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(for example from Example V-1) in 15 ml of dichloromethane was admixedfirst with 0.75 ml (0.55 g; 5.4 mmol) of triethylamine and then with 4ml (0.41 g; 4.32 mmol) of chloromethyl ethyl ether. After the mixturehad been stirred overnight, approximately 50% of starting material werestill present (TLC). A further 0.25 ml of triethylamine and 0.17 ml ofthe ether were introduced. Since no further reaction could be detected,another 0.25 ml of triethylamine was added and the mixture was heated tothe boil. For work-up, the reaction mixture was extracted with 10%strength citric acid and 1N aqueous sodium hydroxide solution, dried,concentrated and chromatographed over a silica gel column (Ø=3 cm, 1=30cm). Elution with cyclohexane/ethyl acetate using a 5-stage gradientfrom 20:1 to 3:1 gave, as second fraction, 0.30 g (17% of theory) of1-ethoxymethyl-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-di-hydro-1H-imidazole(I-6a) and, as third fraction, 0.34 g (20% of theory) of3-ethoxymethyl-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-di-hydro-3H-imidazole(I-6b).

(I-6a): ¹H NMR (400 MHz, DMSO): δ [ppm] 1.0 (t, 3H); 3.2-3.5 (m, 2+1H);4.1 (m, 1H); 4.4 (s, 1H); 5.3 (m, 1H); 7.2-7.9 (m, 11H);

(I-6b): ¹H NMR (400 MHz, DMSO): δ [ppm] 0.9 (t, 3H); 3.1-3.3 (m, 2H);3.7 (m, 1H); 4.2 (m, 2H); 4.4 (m, 1H); 5.1 (m, 1H); 7.2-7.9 (m, 11H);

Example I-7

1.5 g (3.6 mmol) of4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(for example from Example V-1) were dissolved in 20 ml of toluene,admixed with 1.7 ml (1.84 g; 18 mmol) of acetic anhydride and boiledunder reflux for 1 h. The mixture was then concentrated and the residuewas recrystallized from a mixture of cyclohexane and ethyl acetate. Thisgave 1.07 g (65% of theory) of1-acetyl-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(I-7a). 0.6 g of concentration residue from the mother liquor wasseparated by column chromatography (silica gel; Ø=3cm, 1=30 cm;cyclohexane:ethyl acetate=5:1). 0.12 g (7% of theory) of3-acetyl4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-3H-imidazole(I-7b) was obtained as second fraction as an oil.

(I-7a): m.p.: 109-111° C; (I-7b): ¹H-NMR (400 MHz, DMSO): δ [ppm] 1.9(t, 3H); 3.7 (m, 1H); 4.6 (m, 1H); 5.6 (m, 1H); 7.2-7.9 (m, 11H).

Example I-8

1.0 g (2.3 mmol) of1-cyano-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(for example from Example I-5, compound I-5a) were initially chargedunder argon in 15 ml of pyridine p.a. At room temperature, hydrogensulphide was introduced for 30 min, the mixture was stirred for another1.5 h and the remaining hydrogen sulphide was subsequently flushed out.For work-up, the mixture was concentrated under reduced pressure,toluene was added and the mixture was reconcentrated. The residue of 1.2g was purified by chromatography (silica gel; Ø=3 cm, 1=30 cm; gradientcyclohexane:ethyl acetate 4:1→1:2). The resulting crystalline productwhich melted at 93-95° C. contained, according to 2D-NMR spectrum andGC-MS, in addition to 10% of the desired4-(4′-trifluoromethoxy4-biphenylyl)-2-(2,6-difluorophenyl)-1-thiocarbamoyl-4,5-dihydro-1H-imidazole,the non- N-substituted imidazoline (V-1).

MS (CI): mnz: 477 (M⁺).

Example I-9

Similarly to Example I-8, 0.5 g (1.15 mmol) of3-cyano-4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-3H-imidazole(for example from Example I-3, compound I-3b) gave 0.50 g of crudeproduct. Column chromatography (silica gel Ø=3 cm, 1=30 cm; gradientcyclohexane:ethyl acetate 8:1→2:1) gave 0.17 g of N-substitutedimidazoline (V-1) which, according to ¹H NMR spectrum and GC-MS,contained small amounts of the desired4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-thiocarbamoyl-4,5-dihydro-3H-imidazole.

MS (CI): m/z: 477 (M⁺).

PREPARATION OF THE PRECURSORS Example II-1

9.8 ml (13.7 g, 0.075 mol) of p-bromostyrene were dissolved in 50 ml ofacetonitrile p.a. and a stream of argon was passed over this mixture. Atfrom 5 to 10° C., a solution of 12 g (0.075 mol) of ethylN,N-dichlorocarbamate in 50 ml of acetonitrile p.a. was added dropwiseat such a rate that the temperature did not exceed 10° C. The mixturewas subsequently stirred at room temperature for another 3 h. After GCreaction control (about 88% of product), 75 ml of a 20% strength sodiumbisulphite solution were added with cooling at from 5 to 10° C.(exothermic reaction). After phase separation, the aqueous phase wasextracted with 2×20 ml of diethyl ether. The combined organic phaseswere extracted with saturated sodium chloride solution and water, driedand concentrated. This gave 22.10 g (96% of theory) of crude ethylN-[2-(4-bromophenyl)-2-chloroethyl]-carbamate which was directly reactedfurther.

M.p.: 61-62° C.

Example V-1

At room temperature, 2 g (4.08 mmol) of4-(4′-trifluoromethoxy-4-biphenylyl)-1-ethoxycarbonyl-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole(for example from Example II-2) were added to a solution/suspension of1.1 g (20 mmol) of potassium hydroxide in 15 ml of ethanol p.a. Themixture was stirred under reflux for one hour and the conversion waschecked by TLC, and the mixture was then cooled, poured into water andextracted with tert-butyl methyl ether. Drying and concentration of thecombined extracts gave 1.7 g of crude product. This was stirred with amixture of dichloromethane and cyclohexane and the precipitate crystalswere filtered off with suction. The mother liquor was concentrated andonce more stirred with a small amount of the mixture, giving a secondcrystal fraction. Yield: 1.00 g (60% of theory) of4-(4′-trifluoromethoxy-4-biphenylyl)-2-(2,6-difluorophenyl)-4,5-dihydro-1H-imidazole.

M.p.: 125-127° C.

USE EXAMPLES Example A

Phaedon larvae test

Solvent: 7 parts by weight of dimethylfornamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration andpopulated with mustard beetle larvae (Phaedon cochleariae) while theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, an active compound concentration of 0.1%, for example thecompounds of Preparation Example I-4, I-5a, I-5b, I-6a, I-6b and I-8showed a kill of 100% and the compound from Preparation Example I-7ashowed a kill of 90%, after 7 days.

Example B

Spodoptera frugiperda test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration andpopulated with caterpillars of the army worm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an active compound concentration of 0.1%, for examplethe compounds of Preparation Examples I-4, I-3, I-5a, I-5b, I-6a, I-7aand I-8 showed, after 7 days, a kill of 100%.

Example C

Tetranychus test (OP-resistant/dip treatment)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed, 0% means that none of thespider mites have been killed.

In this test, after 7 days, for example the compounds of PreparationExamples I-3, I-5a, I-5b, I-6a and I-7a showed, at an active compoundconcentration of 0.01%, a kill of 100%, and the compound of PreparationExample I-8 showed a kill of 95%.

Example D

Blowfly larvae test/development-inhibitory action

Test animals: Lucilia cuprina larvae

Solvent: Dimethylsulfoxide

20 mg of active compound are dissolved in 1 ml of dimethyl suiphoxide,and more dilute concentrations are prepared by dilution with dist.water.

Approximately 20 Lucilia cuprina larvae are introduced into a test tubewhich contains approximately 1 cm³ of horse meat and 0.5 ml of theactive compound preparation to be tested. After 24 and 48 hours, theefficacy of the preparation of active compound is determined. The testtubes are transferred into a beaker with sand-covered bottom. After afurther 2 days, the test tubes are removed and the pupae are counted.

The effect of the preparation of active compound is assessed by thenumber of the flies which have hatched after 1.5 times the developmenttime of an untreated control. 100% means that none of the flies havehatched; 0% means that all flies have hatched normally.

In this test, the compounds of preparation examples I-3 and I-4a showed,at an active compound concentration of 100 ppm, an efficacy of 100%.

What is claimed is:
 1. Compounds of the formula (I)

in which Ar¹ represents the grouping (a)

 in which R² represents halogen, alkyl, alkoxy or halogenoalkoxy and R²represents hydrogen, halogen, alkyl or alkoxy, Ar² represents thegrouping (b) or (c)

 in which R³, R⁴, R⁵ and R⁶ independently of one another each representhydrogen, halogen, alkyl, alkoxy, halogenoalkoxy or halogenoalkylthio,R⁷ represents hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy or halogenoalkylthio and Y represents adirect bond, oxygen, methylene, —O—CH₂— or —CH₂O— and R representscyano, alkoxyalkyl, formyl, alkylcarbonyl, alkoxycarbonyl or —C(X)—NHR⁸in which X represents oxygen or sulphur and R⁸ represents hydrogen oralkyl.
 2. Compounds of the formula (I) according to claim 1 in which Ar¹represents the grouping (a)

 in which R¹ represents halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy orC₁-C₃-halogenoalkoxy and R² represents hydrogen, halogen, C₁-C₃-alkyl orC₁-C₃-alkoxy, Ar² represents the grouping (b) or (c)

 in which R³, R⁴, R⁵ and R⁶ independently of one another each representhydrogen, halogen, C₁-C₁₂-alkyl or C₁-C₁₂-alkoxy, R⁷ representshydrogen, halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,C₁-C₆-halogenoalkyl, C₁-C₄-halogenoalkoxy or C₁-C₄-halogenoalkylthio, Yrepresents a direct bond or oxygen and R represents cyano,C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl or—C(X)—NHR⁸ in which X represents oxygen or sulphur and R⁸ representshydrogen or C₁-C₄-alkyl.
 3. Compounds of the formula (I) according toclaim 1 in which Ar¹ represents the grouping (a)

 in which R¹ represents fluorine, chlorine, bromine, iodine, C₁-C₃-alkyland C₁-C₃-alkoxy and R² represents hydrogen, fluorine, chlorine,bromine, C₁-C₃-alkyl or C₁-C₃-alkoxy, Ar² represents the groupings (b-a)or (c-a)

 in which R³, R⁴, R⁵ and R⁶ independently of one another each representhydrogen, fluorine, chlorine, bromine, iodine, C₁-C₆-alkyl orC₁-C₆-alkoxy, R⁷ represents hydrogen, fluorine, chlorine, bromine,iodine, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, fluorine- orchlorine-substituted C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio, Rrepresents cyano, C₁-C₃-alkoxy-C₁-C₃-alkyl, C₁-C₃-alkylcarbonyl,C₁-C₂-alkoxycarbonyl or —C(X)—NHR⁸ in which R⁸ represents hydrogen orC₁-C₄-alkyl, X represents oxygen or sulphur.
 4. Compounds of the formula(I) according to claim 1 in which Ar¹ represents the grouping (a-1),(a-2) or (a-3)

 in which R¹ represents fluorine, chlorine, bromine, methyl, ethyl,methoxy or ethoxy and R² represents hydrogen, fluorine, chlorine,bromine, methyl, ethyl, methoxy or ethoxy, Ar² represents the grouping(b-b) or (c-b)

 in which R³, R⁴, R⁵ and R⁶ independently of one another each representhydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl,methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,tert-butoxy, pentyloxy or hexyloxy, R⁷ represents fluorine, chlorine,bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio,isopropylthio, difluoromethyl, trifluoromethyl, dichloromethyl,trichloromethyl, difluoromethoxy, trifluoromethoxy,chlorodifluoromethoxy, 1,1-difluoroethoxy, 1,1,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy,2,2,2-trichloro-1,1-difluoroethoxy, pentafluoroethoxy,difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio,1,1-difluoroethylthio, 1,1,2-trifluoroethylthio,2,2,2-Trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio,2-chloro-1,1,2-trifluoroethylthio, 2,2,2-trichloro-1,1-difluoroethylthioor pentafluoroethylthio, R represents cyano, ethoxymethyl, acetyl,propionyl, butyryl, methoxycarbonyl, ethoxycarbonyl or —C(X)NHR⁸ inwhich R⁸ represents hydrogen, methyl or ethyl, X represents oxygen orsulphur.
 5. Process for preparing compounds of the formula (I) accordingto claim 1, characterized in that A) diphenylimidazolines of the formula(I-a)

 in which Ar¹ and Ar² are each as defined above and R⁹ representsC₁-C₄-alkyl, are obtained by condensing β-chlorocarbamates of theformula (II)

 in which Ar² and R⁹ are each as defined above with benzonitriles of theformula (III) Ar¹—CN  (III),  in which Ar¹ is as defined above in thepresence of sulphuric acid, or B) diphenylimidazolines of the formula(I-b)

 in which R is as defined above and R¹⁻¹ represents fluorine, chlorine,alkyl, alkoxy or halogenoalkoxy, R²⁻¹ represents hydrogen, fluorine,chlorine, alkyl or alkoxy, R⁵⁻¹ and R⁶⁻¹ independently of one anothereach represent hydrogen, fluorine, chlorine, alkyl, alkoxy,halogenoalkyl or halogenoalkylthio and R⁷⁻¹ represents hydrogen,fluorine, chlorine, cyano, alkyl, alkoxy, alkylthio, halogenoalkyl orhalogenoalkylthio are obtained by coupling halogen compounds of theformula (I-c)

 in which R, R¹⁻¹, R²⁻¹ and R⁵⁻¹ are each as defined above and Zrepresents bromine or iodine with boronic acids of the formula (IV)

 in which R⁶⁻¹ and R⁷⁻¹ are each as defined above in the presence of acatalyst and, if appropriate, in the presence of an acid binder and, ifappropriate, in the presence of a diluent, or C) diphenylirnidazolinesof the formula (I)

 in which Ar¹, Ar² and R are each as defined above are obtained bycondensing diphenylimnidazolines of the formula (V)

 which are not substituted at nitrogen and in which Ar¹ and Ar² are eachas defined above with compounds of the formula (VI) R—X¹  (VI),  inwhich R is as defined above and X¹ represents, depending on the radicalR, a suitable leaving group in which R¹⁰ represents alkyl or aryl, ifappropriate in the presence of a reaction auxiliary, or D)diphenylirnidazolines of the formula (I-d)

 in which Ar¹, Ar² and X are each as defined above are obtained byreacting nitrites of the formula (I-e)

 in which Ar¹ and Ar² are each as defined above with water or hydrogensulphide, if appropriate in the presence of a reaction auxiliary. 6.Compounds of the formula (V)

in which Ar¹ represents the grouping (a)

 in which R¹ represents halogen, alkyl, alkoxy or halogenoalkoxy and R²represents hydrogen, halogen, alkyl or alkoxy, A² represents thegrouping (b) or (c)

 in which R³, R⁴, R⁵ and R⁶ independently of one another each representhydrogen, halogen, alkyl, alkoxy, halogenoalkoxy or halogenoalkylthio,R⁷ represents hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy or halogenoalkylthio and Y represents adirect bond, oxygen, methylene, —O—CH₂— or —CH₂O—.
 7. A pesticidecomprising one or more of the compounds of claim 1 and a member selectedfrom the group consisting of liquid solvents, solid carriers,surface-active agents and mixtures thereof.
 8. A method for controllingpests selected from the group consisting of insects, arachnids andnematodes comprising allowing an effective amount of one or morecompounds of claim 1 to act on said pests and/or their habitat.
 9. Aprocess for preparing a pesticide comprising mixing one or more of thecompounds of claim 1 with a member selected from the group consisting ofliquid solvents, solid carriers, surface-active agents and mixturesthereof.